TWI440709B - Composition, method and use - Google Patents

Description

Composition, method and use

The present invention relates to an additive composition for fuel supply, a fuel composition, and a method and use of such a composition. In particular, the present invention relates to additive compositions that can be used to achieve improved fuel economy and allow the use of heavier and/or more dirty fuels to replace lighter and/or cleaner fuels.

Background of the invention

As crude oil prices rise, all downstream products become more expensive - for example, for heating, power plants and vehicles, especially ships.

Higher refining or "lighter" fuels are less expensive than "higher" or "heavier" fuels. Less preferred to use the latter. These are more viscous and tend to burn more dirty. These tend to separate or settle during transport, blending or storage. By "dirty", we mean that highly refined fuels contain higher concentrations of unstable components or compounds than highly refined fuels. Such components or compounds promote the formation of deposits or deposits within the fuel. Furthermore, it is believed that such components or compounds cause harmful carbon formation upon combustion, particularly resulting in reduced efficiency of deposits, combustion, and waste heat recovery of the fuel injection pump.

In many commercial haulage sectors, fuel costs are a major part of total operating costs. In the case of commercial transportation, for example, the estimated fuel cost sometimes reaches 70% of the total operating cost of the ship.

Therefore, there is often a strong economic driving force that favors less refined fuel, but it is stopped by the above-mentioned adverse consequences. For example, ship operators cannot tolerate the extras of ship engines and related equipment in removing soot (ie carbon) deposits. Downtime. Moreover, many ships cannot have a smoke exhaust stream visible to the naked eye. This is unacceptable on cruise ships and in any case does not meet the environmental regulations of the country where the ship may be docked.

Blended fuels - for example, conventional diesel and bio-, oil, and different grades of conventional fuel oils - may also suffer from instability problems. This is a particular problem when the ship purchases fuel in the spot market and adds the purchased fuel to the fuel remaining in the fuel depot. As a result, problems may occur when starting and/or burning.

What is desired is to obtain an additive composition that reduces or overcomes such problems.

The object of a particular embodiment of the invention is to provide an additive composition that provides benefits when utilizing a fuel having a viscosity of 40 ° C as low as 1 cSt.

An object of particular embodiments of the present invention is to provide an additive composition that provides benefits when utilized with a fuel having a viscosity of 40 ° C up to 1000 cSt.

The object of a particular embodiment of the invention is to provide an additive composition that allows the use of heavier fuels in the case of previously used lighter fuels; reduces or avoids undesired adverse consequences; in particular reduces or avoids, for example, leads to Harmful carbon formation from carbon deposition and/or smoke exhaust.

The target improvement of the specific examples of the present invention may suffer from stability problems - for example, phase separation, or separation or coagulation of the polyaromatic compounds within the fuel, or the stability of the settling fuel.

The object of a particular embodiment of the invention is to improve the delivery of fuel to a combustion site, for example, to improve its flow characteristics.

The object of a specific example of the present invention is to improve the transportation of fuel to a combustion site, For example, about its uniformity or burning cleanliness.

The additive composition of the present invention contains a metal compound (as defined later) which may be ferrocene.

Ferrocene and its derivatives are known in the literature. Ferrocene and its manufacture were first described in Nature 168 (1951), Page 1039. Since then, ferrocene and its derivatives and corresponding manufacturing processes have been the subject of numerous patents, such as US 2 769 828, US 2 834 796, US 2 898 360 and US 3 437 634.

In addition to many other compounds, DE 34 18 648 lists ferrocene (dicyclopentadienyl iron) as a possible additive for optimizing the combustion of heating oils. This optimized combustion stimulates complete combustion of the heated oil.

In US 4 389 220 a two-stage method of adjusting a diesel motor is illustrated. According to this patent, the initial high dose of ferrocene in the diesel fuel is from 20 to 30 ppm - the carbon deposits in the combustion chamber can be removed and a layer of catalytic iron oxide is also deposited on the combustion surface. Next, a lower dose of ferrocene -10 to 15 ppm - maintains the catalytic iron oxide coating. It has also been found that by such means, fuel consumption is reduced by up to 5%. Since it is difficult to add an organic iron compound in a solid form such as ferrocene to a fuel, a concentrate is generally used.

The additive composition of the present invention contains an organic compound (as defined later) which may be camphor.

DE 30 31 158 A1 teaches that a mixture of 70 to 85 vol% water and 0.1 to 1% camphor can be added to the heating oil shortly before combustion.

DE 21 47 994 teaches that additives containing camphor in particular can be used internally The combustion air of the gas turbine.

US 3 925 031 teaches that additives containing camphor and naphthalene in particular can be added to gasified fuels, diesel fuels or lubricating oils.

In the art, camphor has been used in fuels to reduce fuel consumption or toxic emissions. However, it is not known that camphor can reduce soot. Conversely, as discussed in US 5 116 390, the disadvantage of using camphor is the formation of additional soot that is noted when burning fuels containing camphor as an additive. Similarly, US 3 925 031 teaches that the use of a sufficient amount of camphor in gasoline to increase the effective octane rating of gasoline results in a decrease in combustion efficiency and a corresponding increase in the amount of unburned carbon, resulting in soot-like effluent.

It is also known that combustion catalysts can lead to the production of ash, see, for example, US 6 948 926. Thus, additives that reduce soot formation may result in increased ash formation. H. Jungbluth, B. Richter, ''Neue Ergebnisse zur Regeneration von Dieselpartikelfiltern mit Additiven", Mineralöltechnik, July 1998; Regeneration von Partikelfiltern mit Additiven, FUELS 1999, 2nd International Colloquium, 20-21.01.1999, page 489-495 The use of such additives in heavy duty diesel engine fuels provides a peak in emissions from the ash produced by the combustion of the additive.

CN 1597873 discloses a fuel comprising methanol, hydrogen peroxide, ferrocene and camphor which reduce harmful emissions.

The additive composition of the present invention contains a stabilizer.

Various proposals have been made to disperse the asphaltene in the fuel. for example: No. 5,073,248 discloses the use of secondary alkyl sulfonic acids as asphalt fines-dispersants. The composition may further comprise: 1. an alkylphenol formaldehyde resin, 2. an alkoxylated amine, 3. a wax-dispersant.

EP0946679A discloses the use of sarcosinate as a bitumen concentrate. The sarcosinate stabilizer can be combined with an alkylphenol formaldehyde resin, an alkoxylated amine, and a sulfonic acid.

WO9904138 discloses asphaltene dispersants using ether carboxylic acid as crude oil.

No. 5,494,607 discloses the use of alkyl substituted phenol-polyethylene polyamine-formaldehyde resins as asphalt fines dispersants.

US 6,270,653 discloses a method for controlling the precipitation of asphalt in a fluid, and a functional group capable of reacting with asphaltene and an alkyl XR coating chemical extending outward to the liquid phase, wherein X is preferably an aryl group and the R system contains 10-25 carbon atoms.

In one aspect, the invention provides an additive composition for use in a fuel, comprising: (i) a metal compound selected from the group consisting of iron compounds, manganese compounds, calcium compounds, cerium compounds, and mixtures thereof; (ii) organic compounds selected from the group consisting of bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate Esters, and mixtures thereof; and (iii) stabilizers.

The stabilizer of the present invention may be suitably selected from the group consisting of asphalt dispersants, wax anti-settling agents, low temperature flow improvers, fuel antioxidants, biofuel instability inhibitors or blended fuel separation inhibitors. Other agents that promote the stability of the composition are not excluded.

In still another aspect, the present invention provides a fuel composition comprising the additive composition of the present invention and a fuel. Suitably, the fuel is a hydrocarbon fuel. The fuel can be petroleum or distilled fuel. The fuel may be a fuel selected from the group consisting of diesel fuel, marine fuel, bottom fuel, heating oil, medium distillate oil and heavy fuel oil; and includes GTL (liquefied gas), CTL (liquefied coal), BTL (liquefied raw) And OTL (liquefied oil sands); or a mixture selected from such (if appropriate).

The fuel may be a so-called recycled fuel or biofuel, for example, biodiesel.

The fuel may be a fuel that tends to separate or settle during transport or storage.

The fuel may be a blended fuel in which the composition of the blend is not completely compatible.

The fuel may be a fuel that is unstable due to oxidation.

The fuel may be a fuel that tends to fully or partially solidify in a surrounding environment.

The fuel can be a fuel that is "dirty" to burn. By this we mean that the fuel produces carbon during combustion and this results in carbon deposits on the surface of the combustion system (hereinafter "coking") and/or visible smoke-like exhaust gases.

As indicated above, the fuel can be a biofuel. It is generally known that biofuels - compared to petroleum based (or distilled) fuels - are less susceptible to oxidation and are less stable. This inherent instability is due to the abundant olefinic (unsaturated) materials in the petroleum-based fuel-biofuel. Contact with air (oxygen) by biofuels or biofuels/distillation blends causes oxidation of the fuel, which in turn causes instability. Fuel oxygen The formation results in the formation of alcohols, aldehydes, ketones, carboxylic acids and further reaction products of such functional groups, some of which may form polymers.

Water is also an important component in promoting biofuel degradation. Because microorganisms produce and utilize enzymes (eg, lipolytic enzymes) in their normal metabolic pathways, such organisms are capable of digesting biofuels and any petroleum fuels that occur, resulting in adverse changes in host composition (eg, formation of precipitates) ()).

Moreover, long-term storage of biofuels and their blends at high temperatures can lead to an increase in the speed of other degradation processes (microorganisms, hydrolysis, oxidation), resulting in more storage instability.

The composition of petroleum fuels that are subsequently blended with biodiesel is also an important factor in fuel instability. Supported data indicate that the propensity of the fuel to form oxidation products will increase in certain fuel blends.

These factors greatly increase the instability of bulk biofuels and biofuel/petroleum fuel blends, especially bulk diesel and biodiesel/petroleum blends. Degradation products of oxidation - such as precipitates and glue - can clog engine nozzles or create unwanted deposits that can cause subsequent engine damage. The unstable oxidation of such fuels is of concern to fuel producers, engine manufacturers and fuel users.

In yet another aspect, the present invention provides a method of combusting a fuel composition in a combustion system with an exhaust pipe, the method comprising providing a fuel composition comprising:

(i) a metal compound selected from the group consisting of iron compounds, manganese compounds, calcium compounds, cerium compounds, and mixtures thereof; (ii) an organic compound selected from the group consisting of bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate, and mixtures thereof; (iii) a stabilizer; and (iv) a fuel; and burning the fuel composition.

In still another aspect, the invention provides the use of the following fuel composition for combustion in a combustion system (i) a metal compound selected from the group consisting of iron compounds, manganese compounds, calcium compounds, antimony compounds, and mixtures thereof; (ii) an organic compound selected from the group consisting of bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate, and mixtures thereof; and (iii) stabilizers; for one or more of the following purposes - reduced Or to prevent coking on the surface of the combustion system; - to reduce or prevent visible smoke from venting the gas; - to make the fuel suitable for the combustion system (not suitable if there is no such additive); - to enhance fuel during storage and / or delivery Stability; - improve fuel combustion efficiency; - improve fuel flow characteristics.

In this specification, when we refer to reducing the formation, deposition or carbon content of carbon, we refer to elemental carbon, which may also be referred to as soot. In the case of exhaust gases, carbon may cause it to be smoky.

When we refer to the combustion system in this manual, we mean straight It is connected to any part of the combustion equipment, such as fuel injection pumps and burners, and downstream parts of the combustion equipment, such as rotors, turbine blades, heat recovery equipment, and exhaust piping.

In one aspect, the task of the present invention is to provide a fuel composition that provides components (i), (ii), and (iii) as defined herein, which fuel composition can be beneficially used in general fuels, but the fuel The composition provides particular advantages in terms of heavy fuels and/or blended fuels, maintaining stability, inhibiting the formation of soot in the combustion surface and/or exhaust gases, and improving combustion performance. After achieving the benefits of the present invention, fuels previously considered unusable for a given combustion system become usable.

Graphical description

Figure 1 shows this plot of three fuels under low load conditions (0 kW).

Additional aspects of the invention are defined below and in the accompanying claims.

Metal compound (i)

The metal compound (i) is selected from the group consisting of an iron compound, a manganese compound, a calcium compound, a hydrazine compound, and a mixture thereof.

It is important that the metal compound (i) used in the present invention is soluble in fuel or dispersible in fuel and is preferably fuel-stable. The exact nature of metal-containing compounds is less important.

Manganese compound

Preferably, the manganese compound, if present, is selected from the group consisting of manganese carbonyl compounds, manganese (II) 2-ethylhexanoate, manganese naphthenate, and mixtures thereof.

The most desirable general type of carbonyl manganese compound used in accordance with the present invention Contains an organic polycarbonyl manganese compound. For best results, a cyclopentadienyl manganese tricarbonyl compound of the type described in U.S. Pat. Nos. 2,828,417 and 3,127,351 is used. Thus, compounds such as cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, ethyl cyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl can be used. , trimethylcyclopentadienyl tricaptan manganese, propyl cyclopentadienyl manganese tricarbonyl, isopropyl cyclopentadienyl manganese tricarbonyl, butyl cyclopentadienyl manganese tricarbonyl, pentyl Cyclopentadienyl trienyl manganese, hexyl cyclopentadienyl manganese tricarbonyl, ethyl methylcyclopentadienyl manganese tricarbonyl, dimethyl octyl cyclopentadienyl manganese tricarbonyl, dodecane A cyclopentadienyl manganese tricarbonyl, a fluorenyl manganese tricarbonyl, and the like, wherein the cyclopentadienyl moiety contains up to about 18 carbon atoms.

In one aspect, the manganese compound is an organomanganese compound.

A preferred organomanganese compound is cyclopentadienyl manganese tricarbonyl. Particularly preferred for use in the practice of this invention is methylcyclopentadienyl manganese tricarbonyl.

The synthesis of cyclopentadienyl manganese tricarbonyl is well documented in the literature. See, for example, the above-mentioned U.S. Pat. Nos. 2,818,417 and 3,127,351 - especially U.S. Pat. Nos. 2,868,816; 2,898,354; 2,960,514; and 2,987,529.

Other useful organomanganese compounds include the mercaptotricarbonyl manganese described in US Pat. No. 2,959,604, such as methyl ethinylcyclopentadienyl manganese tricarbonyl and benzhydryl methylcyclopentadienyl tricarbonyl. Manganese; an aryl pentacarbonyl manganese as described in US Pat. No. 3,007,953, such as phenylpentacarbonyl manganese; and an aromatic cyanodicarbonyl manganese as described in US Pat. No. 3,042,693, such as manganese trimethyl cyanide. Also, it can be used to make the RMn(CO) ₂ L type of cyclopentane

An alkenyl dicarbonyl manganese compound, wherein R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms, and L is a ligand such as an olefin, an amine, a phosphine, a SO ₂ , a tetrahydrofuran, or the like Things. Such compounds are mentioned, for example, in Herberhold, M., Metal π-Complexes, Vol. II, Amsterdam, Elsevier, 1967 or Giordano, PJ and Weighton, MS, Inorg. Chem., 1977, 16, 160 and. Manganese pentacarbonyl dimer (decacarbonyl dimanganese) can also be used if necessary.

Preferably, the manganese compound is a manganese complex.

Preferably, the manganese compound is selected from the group consisting of a cyclopentadienyl tri-based manganese and a substituted cyclopentadienyl manganese tricarbonyl.

The manganese compound may be cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl, wherein the substituent may be, for example, one or more C _1-5 alkyl groups, preferably C. _1-2 alkyl. Combinations of such manganese complexes can also be used.

Preferably, the manganese compound is selected from the group consisting of cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl.

Preferably, the manganese compound is methylcyclopentadienyl manganese tricarbonyl (MMT).

Calcium compound

Preferably, the calcium compound, if present, is selected from the group consisting of calcium 2-ethylhexanoate, calcium naphthenate, calcium sulfonate, calcium carbonylate (including calcium soap, which includes natural calcium soap and high alkali calcium soap) ; and mixtures thereof.

Preferably, the calcium compound is calcium sulfonate.

Other suitable calcium compounds are disclosed in GB 2248068 and GB 2254610 and are discussed in these documents.

Bismuth compound

Preferably, the cerium compound, if present, is selected from the group consisting of cerium (III) 2-ethylhexanoate, cerium sulfonate, cerium lanthanum hydride (including cerium soap, which includes natural cerium soap and high alkali cerium soap); Its mixture.

Iron compound

A single iron compound can be provided as the metal compound (i), or a mixture of iron compounds.

Preferably, the iron compound, if present, is an iron complex selected from the group consisting of bis-cyclopentadienyl iron; substituted bis-cyclopentadienyl iron; iron carboxylate (including iron soap, It includes high alkali iron soaps such as iron tallate and iron octoate; and mixtures thereof.

Preferably, the iron compound is an iron complex selected from the group consisting of bis-cyclopentadienyl iron, substituted bis-cyclopentadienyl iron, and mixtures thereof.

Preferably, the iron compound is a substituted bis-cyclopentadienyl iron selected from the group consisting of adamantyl bis, cyclopentadienyl iron, dicarbonyl bis(dicyclopentadienyl-iron), and mixture. Dicarbonyl bis(dicyclopentadienyl-iron) is also known as a dicarbonylcyclopentadienyl iron dimer.

In one aspect, the iron compound is an iron complex selected from the group consisting of bis-cyclopentadienyl iron, adamantyl bis-cyclopentadienyl iron, dicarbonyl bis(dicyclopentadienyl)- Iron), iron oleate and iron octoate; and mixtures thereof.

Other suitable substituted bis-cyclopentadienyl iron complexes are those wherein the substituent may be, for example, one or more C _1-30 alkyl groups, preferably C _1-20 alkane. The group is preferably a C _1-10 alkyl group, a C _1-5 alkyl group, preferably a C _1-2 alkyl group. Combinations of such iron complexes can also be used.

A suitable alkyl-substituted-dicyclopentadienyl iron complex is cyclopentadiene (methylcyclopentadienyl) iron, cyclopentadienyl (ethyl-cyclopentadienyl) iron, bis-(methylcyclopentadienyl) iron, bis-(ethylcyclopentane Alkenyl) iron, bis-(1,2-dimethyl-cyclopentadienyl)iron, and bis-(1-methyl-3-ethylcyclopentadienyl)iron. The iron complexes can be prepared by the procedures taught in US-A-2, 680, 756, US-A-2, 804, 468, GB-A-0733, 129 and GB-A-0763550. Other volatile iron complexes are iron pentacarbonyl.

Suitable iron complexes are bis-cyclopentadienyl iron and/or bis-(methylcyclopentadienyl) iron.

Coordination chemistry for transition metals (including iron) in hydrocarbon solvents such as diesel fuels is well known to those skilled in the art (see, for example, WO-A-87/01720 and WO-A-92/20762).

The substituted bis-cyclopentadienyl complex (substituted ferrocene) used in the iron of the present invention includes the complex of the substituents which may be located in one or both of the cyclopentadienyl groups. Suitable substituents include, for example, one or more C _1-5 alkyl groups, preferably C _1-2 alkyl groups.

Particularly suitable alkyl-substituted-dicyclopentadienyl iron complexes (substituted ferrocenes) include cyclopentadienyl (methylcyclopentadienyl) iron, bis-(methylcyclopentyl) Dienyl) iron, bis-(ethylcyclopentadienyl) iron, bis-(1,2-dimethylcyclopentadienyl) iron and 2,2-diethylferrocenyl-propane .

Other suitable substituents which may be present on the cyclopentadienyl ring include cycloalkyl (e.g., cyclopentyl), aryl (e.g., o-tolylphenyl), and fluorenyl, for example, in the presence of diethenyl iron. A particularly advantageous substituent is hydroxyisopropyl which produces (?-hydroxyisopropyl)ferrocene. (α-Hydroxyisopropyl)ferrocene is a room temperature liquid as disclosed in WO-A-94/09091.

A ferrocene connected by a "bridge" can be used in the present invention. Suitable compounds are taught in WO 02/018398 and WO 03/020733. Thus, a suitable "bridge" to which ferrocene is attached can be an unsubstituted or substituted hydrocarbon group. The term "unsubstituted or substituted hydrocarbyl" as used in this context is intended to mean a radical comprising at least C and H and optionally includes one or more suitable substituents. In a preferred embodiment, one carbon atom of the hydrocarbyl "bridge" is attached to the two ferrocene moieties and, therefore, ferrocene is bridged. The additional ferrocene moieties can be attached via additional hydrocarbyl "bridges". A typical unsubstituted or substituted hydrocarbyl group is an unsubstituted or substituted hydrocarbon group. The term "hydrocarbon" as used herein refers to any of alkyl, alkenyl and alkynyl groups which may be straight chain, branched or cyclic, or aryl. For example, the unsubstituted or substituted hydrocarbyl group can be an alkylene group, a branched alkyl group or a cycloalkyl group. The term hydrocarbon also includes such groups, but wherein the groups have been selectively substituted. If the hydrocarbon is a branched structure having a substituent(s) thereon, the substitution may be on the hydrocarbon backbone or on the branch; alternatively, the substitution may be on the hydrocarbon backbone and on the branch. Preferred unsubstituted or substituted hydrocarbyl groups are unsubstituted or substituted alkylene groups having at least one carbon atom in the alkylene linkage. More preferably, the unsubstituted or substituted hydrocarbyl group is an unsubstituted or substituted alkylene group having from 1 to 10 carbon atoms in the alkylene linkage, for example, having at least 2 in the alkylene linkage One carbon atom or one carbon atom in the alkylene bond. In case the hydrocarbyl group contains more than one C, the carbons do not need to be connected to each other. For example, at least two of the carbons may be linked via a suitable element or group. Thus, the hydrocarbon group may contain a hetero atom. Suitable hetero atom It is highly apparent to those skilled in the art and includes, for example, sulfur, nitrogen and oxygen, for example, oxygen.

Other organometallic complexes of iron can also be used in the present invention as long as they are soluble in fuel and stable. Such complexes include, for example, five types of base iron, hexacarbonyldiiron, (1,3-butadiene)-tricarbonyl iron, and (cyclopentadienyl)-dicarbonyl iron dimer. . Salts such as bis-tetrahydronaphthalene tetraphenylborate (Fe(C ₁₀ H ₁₂ ) ₂ (B(C ₆ H ₅ ) ₄ ) ₂ ) can also be used.

A preferred iron complex is ferrocene (i.e., bis-cyclopentadienyl iron).

In addition to ferrocene, an equivalent amount of other organic iron compound that is soluble in the hydrocarbon mixture can be used in accordance with the iron content. This application is to all statements and descriptions below. Dicyclopentadienyl iron systems have proven to be particularly suitable. Ferrocene derivatives can be used to at least partially replace ferrocene. A ferrocene derivative is a compound that finds another substituent on one or two cyclopentadienyl rings starting from a basic ferrocene molecule. Examples are ethyl ferrocene, butyl ferrocene, acetyl ferrocene and 2,2-bis-ethylferrocenylpropane. For example, the pairs of Gemini bisferrocenylalkanes described in DE 201 10 995 and DE 102 08 326 are also suitable.

The substituted ferrocene is a preferred iron compound for use in the present invention in combination with its solubility, stability, high iron content, and especially volatility. On this basis, ferrocene itself is a particularly good iron compound. With suitable purity ferrocenyl series sold usable form, such as with a solution PLUTOcen ^RTM Satacen ^RTM, are Innospec Limited. The sold.

The iron compound used in the present invention does not need to be characterized by iron-carbon bonds to be compatible with fuel and stable. Salts can be used; these can be neutral or overbased. to Yes, for example, an overbased soap comprising iron stearate, iron oleate, and iron naphthenate can be used. The preparation of metal soaps is described in The Kirk-Othmer Encyclopaedia of Chemical Technology, 4th Ed, Vol. 8: 432-445, John Wiley & Sons, 1993. Suitable stoichiometric or neutral for use in the present invention, the iron carboxylate comprises the so-called "drier-iron" species, such as tris(2-ethylhexanoate)iron [19583-54-1].

Iron complexes which are not characterized by metal-carbon bonds and which are not prepared as described above may also be used in the present invention provided that they have suitable fuel compatibility and stability. Examples include complexes with beta-diketone esters such as tetramethyl pimelate.

The following iron complexes of chelating ligands are also suitable for use in the present invention: Aromatic Mannich bases, such as those prepared by reacting an amine with an aldehyde or a ketone followed by a nucleophilic attack on the active hydrogen-containing compound, such as two equivalents (tetrapropenyl) phenol, two parts of formaldehyde The reaction product with a portion of ethylenediamine, Hydroxy aromatic oxime, for example (polyisobutenyl)-salicylaldoxime. These can be prepared by the reaction of (polyisobutenyl) phenol, formaldehyde and hydrazine; Schiff bases, such as those prepared by a condensation reaction between an aldehyde or a ketone (such as (tertiary butyl)-salicylaldehyde) and an amine (such as dodecylamine). The tetradentate ligand can be prepared by using ethylenediamine (half equivalent) instead of dodecylamine; a substituted phenol, such as 2-substituted-8-quinolinol, for example 2-dodecenyl-8-quinolinol or 2-N-dodecenylamino-cresol; Substituted phenols, such as those wherein NR ₂ or SR, wherein R is a long chain (e.g., 20-30 C atoms) hydrocarbyl group. In the case of α- and β-substituted phenols, the aromatic ring may advantageously be further substituted with a hydrocarbyl group such as a lower alkyl group; a carboxylic acid ester, especially a succinate, such as those prepared by reacting an acid anhydride such as dodecenyl succinic anhydride with a single equivalent of an alcohol such as triethylene glycol; Deuterated amine. These can be prepared by a variety of methods well known to those skilled in the art. However, particularly useful chelates are the alkenyl substituted succinates, such as dodecenyl succinic anhydride, and amines such as N,N'-dimethylethylenediamine or methyl-2-methyl Prepared by the reaction of the amino group-benzoate; Amino acids, for example, are prepared by reacting an amine such as dodecylamine with an alpha, beta-unsaturated ester such as methyl methacrylate. In the case of using a primary amine, this subsequent can be, for example, chlorinated with oleic acid or oleic acid; Hydroxamic acid, such as those prepared by the reaction of hydrazine and oleic acid, Connecting a phenol, such as those prepared by condensation of an alkylated phenol and an aldehyde (preferably having 1 to 22, preferably 1 to 7 carbon atoms, for example, formaldehyde); Alkylation, substituted pyridine, such as 2-carboxy-4-dodecylpyridine; Boride deuterated amine. These may be prepared by the reaction of a succinic acid oximeing agent such as poly(isobutylene) succinic acid, and an amine such as tetraethylamamine. This process is followed by boronation with boron oxide, boron halide, or boric acid, decylamine or ester. A similar reaction with phosphoric acid produces a phosphorus-containing halogenated amine, which is also suitable for providing an oil-soluble iron chelate for use in the present invention; A pyrrole derivative wherein the alkylated pyrrole is substituted at the 2-position with OH, NH ₂ , NHR, CO ₂ H, SH or C(O)H. Particularly suitable pyrrole derivatives include 2-carboxy-t-butylpyrrole; a sulfonic acid, such as those of the formula R ¹ SO ₃ H, wherein R ¹ is a C ₈ to C ₆₀ hydrocarbon group, such as dodecylbenzene sulfonic acid; An organometallic complex of iron, such as ferrocene, substituted ferrocene, iron naphthenate, iron succinate, stoichiometric or high alkali iron soap (carboxylate or sulfonate), iron picrate, Iron carboxylate and iron diketonate complex.

Suitable picric acid irons for use in the present invention include those disclosed in US-A-4,370,147 and US-A-4,265,639.

Other iron-containing compounds for use in the present invention include those having the formula M(R)x.nL, wherein: M is an iron cation; R is a residue of the organic compound RH, wherein R is contained and can be substituted by a metal M and linked An organic group to the active hydrogen atom H of the O, S, P, N or C atom in the R group; x is 2 or 3; n is 0 or a positive integer indicating the formation of a coordinate bond with the metal cation The number of ligands in the body; and L is a species that can be used as a Lewis base.

Preferred metal compound (i)

Preferably, the metal compound (i) is selected from one or more of iron compounds, methylcyclopentadienyl manganese tricarbonyl, manganese (II) 2-ethylhexanoate, manganese naphthenate, 2-ethyl Calcium hexanoate, calcium naphthenate, calcium sulfonate, cerium (III) 2-ethylhexanoate, cerium sulfonate, and mixtures thereof.

Preferred metal compounds (i) are iron compounds, especially ferrocene.

Organic compound (ii)

The organic compound (ii) is selected from the group consisting of bicyclomonoindole, substituted bicyclic monoterpene, adamantane, propylene carbonate, and mixtures thereof.

Preferably, the organic compound (ii) is selected from the group consisting of bicyclic monoterpenes, substituted doubles Ring monoterpenes, and mixtures thereof.

Suitable substituted bicyclic monoterpenes are those wherein the substituents can be, for example, one or more aldehyde, ketone, alcohol, acetate and ether functional groups.

Preferably, the organic compound (ii) is a bicyclic monoterpene or a substituted bicyclic monoterpene selected from the group consisting of camphor, camphene, isodecyl acetate, dipropylene glycol-isodecyl ether, and mixtures thereof .

In one aspect, the organic compound (ii) is selected from the group consisting of camphor, decene, isodecyl acetate, dipropylene glycol-isodecyl ether, adamantane, propylene carbonate, and mixtures thereof.

Preferably, the organic compound (ii) is camphor. Camphor has a systematic designation of 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one. Camphor has the following structure:

Stabilizer (iii)

Stabilizers are compounds that act to maintain fuel homogeneity and therefore fluidity.

Asphalt concentrate as stabilizer (iii)

Compounds suitable for use in the present case as stabilizer (iii) include bitumen concentrates.

Asphalt fines can result in loss of uniformity and fluidity by promoting internal separation or settling of the fuel, and ultimately, loss of fuel stability. In this case, the asphalt fine dispersant acts to disperse the asphaltene in the fuel.

Ultimately, the goal is to prevent bitumin from causing flow problems, or to separate, or settle, to prevent the surface from becoming coke or to form carbon condensate that is visible as "smoke" in the exhaust gas. It is generally believed that the asphalt fine dispersant forms a three-dimensional layer around the asphaltene, and the asphalt fine dispersant tends to be aromatic and usually a resin. The asphalt fine dispersant appears to inhibit the formation of a bitumen-rich mud. It is believed that when a fuel containing well-dispersed asphaltenes is burned, the asphaltenes burn more completely, eventually becoming carbon dioxide, rather than soot and carbon monoxide. Ingredients (i) and (ii) contribute to an excellent, clean burning. However, although I have a theory explaining the benefits of the present invention, I am not limited to this theory. The present invention relies on the discovery that the compounds of formula (i), (ii) and (iii) work together to provide the above benefits - especially the discovery that the more dirty fuels can be used for the useful benefits of the previously considered necessity of using lighter fuels.

Suitable asphalt fine dispersants for use in the present invention include alkoxylated fatty amines or derivatives thereof; alkoxylated polyamines; alkylsulfonic acids; arylsulfonic acids; sarcosinates; ether carboxylic acids; Carboxylic acid and its derivatives; alkylphenol-aldehyde resin; hydrophilic-lipophilic vinyl polymer; alkyl-substituted phenol polyethylene polyamine formaldehyde resin; alkyl aryl compound; alkoxylated amine and alcohol; Imine; guanamine; zwitterionic compound; fatty acid ester; lecithin and its derivatives; and succinic anhydride and succinimide derivatives.

Preferred asphalt dispersants for use in the present invention are alkyl groups containing an alkyl group, preferably having at least 12 carbon atoms, and selected from, for example, sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, amines, A molecule of a polar functional group of a guanamine, an imine, an alcohol, and an ester. Compounds including aromatic moieties are also suitable. The block of the molecule may, for example, be a polyalkoxy unit, a carbonate group, an imine or a guanamine group. Group connection.

Suitable compounds are polymeric or oligomeric compounds. Most suitable are polymeric or oligomeric compounds comprising hydrophobic and hydrophilic functionalities.

Suitable alkoxylated fatty amines include those of the following formula (i):

Wherein n is an integer from 1 to 4, wherein when n is 1, A has the structure (a); when n is 2, A has the structure (b); when n is 3, A has the structure (c) and When n is 4, A has the structure (d):

And wherein R is a C ₆ to C ₂₂ alkyl group, preferably a C ₆ to C ₁₈ alkyl group; m is 2, 3 or 4, preferably 2 or 3; and x is 5 to 120, preferably 10 to 80. The number; and R ¹ may be H, CH ₃ or both. When both are present, the oxyalkylene moiety may be arranged arbitrarily or in blocks.

Suitable sulfonic acid derivatives for use as asphalt dispersants include alkyl sulfonic acids, aryl sulfonic acids, alkyl aryl sulfonic acids, and derivatives thereof, for example, those of formula (ii): )RSO ₃ X

Wherein X is hydrogen or an alkali metal ion; and R is an optionally substituted linear or branched alkyl group having 2 to 40 carbon atoms, preferably 5 to 30 carbon atoms; or optionally substituted a group having up to 30 carbon atoms. Preferred aryl groups are those based on naphthalene or especially benzene.

In a preferred embodiment, R is an alkylaryl sulfonic acid wherein R is R ¹ Ar ¹ , wherein R ¹ is an alkyl group having 12 to 32, especially 12 to 24 carbon atoms and Ar ¹ is disubstituted The aryl moiety is preferably C ₆ H ₄ .

Also preferred are secondary alkyl sulfonic acids wherein R has from 8 to 22, preferably from 11 to 18 carbon atoms.

Preferred sarcosinates for use as asphalt dispersants in the present invention include those of formula (iii):

Wherein R ¹ and R ² are independently selected from alkyl groups having 1 to 30 carbon atoms which are optionally substituted. Preferably, R ¹ is C ₇ to C ₂₁ alkyl or alkenyl and R ² is H, methyl, butyl, isobutyl or C ₁₁ to C ₂₂ alkyl.

Suitable ether carboxylic acids for use as asphalt dispersants in the present invention include those wherein the optionally substituted hydrocarbyl moiety is attached to the carboxylic acid residue by one or more alkoxy groups. Examples of preferred ether carboxylic acid compounds include compounds of formula (iv): (iv) RO(CH ₂ CHR ¹ O) _x (CH ₂ CHR ² O) _y CH ₂ COOH

Wherein R is C ₂ to C ₃₀ , preferably C ₆ to C ₂₂ , preferably C ₉ to C ₁₈ alkyl or alkenyl, or C ₂ to C ₃₀ , preferably C ₆ to C ₂₀ alkylaryl; R1 Independent of R2, H or CH3, preferably H; and x and y are independently from 0 to 30, preferably from 0 to 20. Preferably, the sum of a and y is between 1 and 20, preferably between 1.5 and 8.

Phosphates suitable for use in the present invention include monoesters, diesters and triesters prepared by the reaction of phosphoric acid with fatty alcohols, alkoxylated fatty alcohols and alkoxylated alkyl aryl alcohols. Preferred phosphate esters include monoesters and diesters of formula (v):

Wherein R ¹ is selected from H, C ₁ to C ₃₀ - preferably C ₁ to C ₂₂ -alkyl, C ₂ to C ₃₀ - preferably C ₂ to C ₂₂ -alkenyl, C ₆ to C ₃₀ Preferred is a C ₆ to C ₁₈ -alkylaryl group or (CH ₂ CHR ³ O) _n R ⁴ wherein R ³ is H or CH ₃ , preferably H, and R ⁴ is H, C ₁ to C ₃₀ Preferred is C ₁ to C ₂₂ -alkyl, C ₂ to C ₃₀ - preferably C ₂ to C ₂₂ -alkenyl, or C ₆ to C ₃₀ - preferably C ₆ to C ₁₈ -alkylalkane a aryl group, and n is an integer of from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10; and R ² is selected from C ₁ to C ₃₀ - preferably C ₁ to C ₂₂ -alkyl C ₂ to C ₃₀ - preferably C ₂ to C ₂₂ -alkenyl, C ₆ to C ₃₀ - preferably C ₆ to C ₁₈ -alkylaryl or (CH ₂ CHR ⁵ O) _m R ⁶ , wherein R ⁵ is H or CH ₃ , preferably H, R ⁶ is H, C ₁ to C ₃₀ - preferably C ₁ to C ₂₂ -alkyl, C ₂ to C ₃₀ - preferably C ₂ to C ₂₂ - The alkenyl group, or C ₆ to C ₃₀ - is preferably a C ₆ to C ₁₈ -alkylalkylaryl group, and m is an integer of from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10. Preferred alkylaryl substituents, if present, are those which are based on benzene or naphthalene and the alkyl and alkenyl substituents may be branched or straight chain and preferably have from 10 to 20, especially 12 Up to 18 carbon atoms.

Suitable carboxylic acids for use as asphalt dispersants are those having more than 4 carbon atoms, especially having from 8 to 22 and especially from 12 to 18 carbon atoms.

Suitable hydrophilic-lipophilic vinyl polymers for use as asphalt dispersants are those of formula (vi):

Wherein each R is independently selected from the group consisting of H and CH ₃ ; each R ¹ is an alkyl, alkenyl, aryl, alkylaryl or arylalkyl group having 2 to 30, preferably 4 to 22 carbon atoms Each Q system is selected from the group consisting of CO ₂ M and CONHR ² , wherein M can be H, a Group I or Group II metal ion, an ammonium or amine cation, a hydroxyethyl group, a hydroxypropyl group or a —(CH ₂ CHRO) _x H And each R ² is -(CH ₂ CHRO) _x H or -(CH ₂ ) _1-3 COOM, wherein x is from 1 to 30, preferably from 1 to 20; and n is a selected integer such that the polymer is obtained It has a weight average molecular weight of between 5,000 and 250,000.

Suitable alkyl-substituted phenol polyethylene polyamine-formaldehyde resins for use as asphalt dispersants include such mono-substituted alkyl phenols having an alkyl substituent having from about 4 to 24 carbon atoms, which may be a linear or branched alkyl group) and a polyethylene polyamine represented by the formula H ₂ N(CH ₂ CH ₂ NH) _n H (wherein n is an integer of 1 to 5); and formaldehyde; an alkylphenol to polyethylene The molar ratio of the amine is from 5:1 to 3:1, and the molar ratio of alkylphenol to formaldehyde is prepared by a base-catalyzed reaction of about 2:1 to 1:2, and the resin has a ratio of from about 1,000 to about 20,000. The weight average molecular weight.

Suitable substituted aromatic compounds for use as asphalt dispersants include those of formula (vii): (vii) X-(R) _n

Wherein n is a valence of from 1 to X, X is a selectively substituted carbocyclic ring, preferably derived from benzene, naphthalene or anthracene and R is preferably an aliphatic chain and has from 10 to 25, preferably from 12 to 20 An alkyl group of carbon atoms.

Suitable asphalt fine dispersants may include a condensation product of a fatty acid having from 12 to 24 carbon atoms and a polyamine of the formula H ₂ N-[(CH ₂ ) _n -NH] _m -R ¹ wherein R ¹ is hydrogen a methyl, ethyl, hydroxyethyl or -(CH ₂ ) _n -NH-R ² group, R ² is hydrogen, methyl, ethyl or hydroxyethyl, and n is between 1 and 4. The number, m represents the number of 1 to 6.

Suitable asphalt fine dispersants can include alkoxylated fatty amines and alkoxylated fatty alcohols. Preferred examples of such include alkoxylated (especially ethoxylated) fatty alcohols having from 8 to 22 carbon atoms and from 10 to 60 moles per mole of fatty alcohol and having from 12 to 22 carbon atoms An alkyl group and an ethoxylated alkylamine having from 10 to 30 moles of ethylene oxide per mole of alkylamine.

Suitable bitumen concentrates may include a compound of formula (viiii) having an imine, thiocarbonyl, or carbonyl group having at least 8, preferably at least 10 carbon atoms:

Wherein Y is a C ₁ -C ₃ difunctional alkyl group, O, S, NR ³ or a deletion; Z is hydrogen, O, S, NR ⁴ or a deletion; W is O, S, or NR ⁵ ; R ¹ , R ² And R ³ , R ⁴ and R ⁵ are independently hydrogen or an organic functional group; and at least one of Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵ is separated from a carbonyl group, a thiocarbonyl group or an imine carbon. At least one polar group of two to ten chemical bonds is substituted. Preferred polar groups are hydroxyl groups and hydroxylamine groups. Preferred organofunctional groups are optionally substituted alkyl, heteroalkyl, aryl, aralkyl, heterocyclic or heterocyclic-alkyl groups. In a preferred embodiment, the at least one organic functional group is a C ₂ -C ₂₂ alkyl group or a heteroalkyl group, more preferably a C ₇ -C ₂₂ alkyl group or a heteroalkyl group, more preferably a C ₉ -C ₂₂ alkane. Or a heteroalkyl group, most preferably a C ₁₅ -C ₂₂ alkyl group. Preferably, the alkyl or heteroalkyl group is unsubstituted.

Suitable asphalt fine dispersants can include the reaction product of an imine and an organic acid. Preferred examples of such asphaltic dispersants are those of carboxylic acids, phosphonic acids or sulfonic acids, especially those having only a single acidic group. Preferably, the salt has a polar group located two to ten chemical bonds from a carbonyl carbon of a carboxylic acid group, a phosphorus atom of a phosphonic acid group or a sulfur atom of a sulfonic acid group; or a nitrogen atom of a protonated imido group. The polar group is preferably selected from the group consisting of hydroxyl, hydrazine, nitro, ester, decylamine or alkylguanamine.

Suitable asphalt fine dispersants can include the reaction product of an amine and an organic acid. Examples of preferred asphalt fine dispersants are salts of carboxylic acids, phosphonic acids or sulfonic acids. Preferably, the salt has a polar group located two to eight chemical bonds from a carbonyl carbon of a carboxylic acid group, a phosphorus atom of a phosphonic acid group or a sulfur atom of a sulfonic acid group; or a protonated amine The nitrogen atom of the base. The polar group is preferably selected from the group consisting of hydroxyl and hydrazine.

Suitable asphalt fine dispersants may include a compound of formula (ix) or a zwitterionic salt thereof:

Wherein R ¹ is C ₁₀ -C ₂₂ alkyl or aralkyl; R ² and R ³ are independently hydrogen or C ₁ -C ₄ alkyl; R ⁴ is hydrogen, C ₁ -C ₂₂ alkyl, C ₇ - C ₂₂ arylalkyl, or -CH(R ⁵ )CH(R ⁶ )COOH, wherein R ⁵ and R ⁶ are independently hydrogen or C ₁ -C ₄ alkyl.

Alkoxy phosphite pitcher (or phosphoalkoxylated asphaltene) can also be used as a bitumen concentrate, as described in US 5,207,891.

Suitable asphalt fine dispersants may include ethylenically unsaturated carboxylic acid esters derived from (A) at least one ethylenically unsaturated alcohol, carboxylic acid or ester, (B) ester having a polar group, and (C) a polymer of structural units of at least one of the ethylenically unsaturated carboxylic acid decylamines, wherein at least one of the structural units contains at least one accompanying cyclic group. Alternatively, the accompanying ring group can be introduced into the polymer by transesterification. Alkyl methacrylates are suitable, for example, C ₆ -C ₂₂ alkyl methacrylates. Two examples of structural units are p-nonylphenyl methacrylate and p-dodecyl phenyl methacrylate.

Suitable asphalt fine dispersants may include esters of C ₆ -C ₃₃ fatty acids, preferably esters of C ₁₀ -C ₂₂ fatty acids. The fatty acid can be saturated (for example lauric acid, stearic acid) or unsaturated (for example oleic acid).

Suitable esters may comprise a first compound (having from 1 to 4, preferably from 1 to 3 acid functional groups) and a second compound (having from 1 to 8, preferably from 1 to 6, more preferably from 1 to 3 hydroxyl groups) a compound formed by the reaction. Depending on the compound selected and its relative amounts, the ester may then comprise additional hydroxyl groups or excess acid groups, or both. The first compound preferably has 4 to 36 carbon atoms, preferably 8 to 24 carbon atoms. The second compound preferably has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.

The ester may, for example, comprise a monooleate, a dioleate, a monostearate, a distearate, a monolaurate or a dilaurate; or, in the case of a sorbitan compound For example, trioleate or tristearate, for example. Particularly preferred are sorbitan esters such as sorbitan monoesters such as sorbitan monooleate, and sorbityl triesters such as sorbitan trioleate. The ester can be alkoxylated, for example, ethoxylated.

Suitable asphalt fine dispersants may include polyethylene glycol fatty acid esters. Examples include esters formed by the reaction of a fatty acid (having 6 to 30, preferably 8 to 24 carbon atoms) and an alcohol (containing 1 to 20 oxidized ethyl units).

Suitable asphalt dispersants include lecithin and lecithin derivatives, for example, soy lecithin.

Suitable asphalt fine dispersants include amber imine and succinic anhydride derivatives having the formula shown in (x):

Wherein R is a selectively substituted alkyl group, which preferably has from 1 to 50 carbon atoms. Most preferably, R is a polyisobutyl chain.

Suitable bitumen concentrates include poly(oxyalkylenes), particularly polyethylene oxide, polypropylene oxide and poly(ethylene oxide/propylene oxide), preferably ethylene oxide/ethylene oxide block copolymers.

Suitable asphalt fine dispersants include phenolic resins. Preferred phenolic resins include compounds of formula (xi):

Wherein m is at least 1; wherein n is at least 1; wherein the or each of R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl, aromatic and heterocyclic, or may be OH, hydrocarbyl, oxygen Base hydrocarbon group, -CN, -NO ₂ , -SO ₃ H, -SO ₂ H, -COOH, -COOR ⁴ , -NH ₂ , -NHR ⁵ , -SO ₂ NH ₂ , -SO ₂ , -NHR ⁶ , CONH ₂ , CONHR ⁷ , SH and halogen; wherein each of R ⁴ , R ⁵ , R ⁶ and R ⁷ is independently selected from a hydrocarbon group. The term "hydrocarbyl" as used in this context means any of an alkyl group, an alkenyl group, an alkenyl group, or a fluorenyl group which may be a straight chain, a branched chain or a cyclic group, or an aryl group. The term hydrocarbyl also includes such groups, but wherein they have been selectively substituted. If the hydrocarbyl group is a branched structure having a substituent(s) thereon, the substitution may be on the hydrocarbon backbone or on the branch; or the substitution may be on the hydrocarbon backbone and on the branch.

In a preferred aspect, m is greater than one. In a preferred aspect, m is from 1 to 50, such as from 1 to 40, from 5 to 30, or from 10 to 20. In a preferred aspect, m is from 11 to 15.

n can be any suitable integer. For example, n can be from 1 to 10, such as from 1 to 8, 1 to 5, 1, 2 or 3. Preferably, n is one.

When n is greater than 1, the "link" group C _n H _2n can be branched.

Preferably, R ^{1 is} not hydrogen.

Preferably, R ¹ is an alkyl group having at least 1 carbon atom, preferably at least 5, or 6, or 7, or 8, or 9 carbon atoms.

Preferably, R ¹ is an alkyl group having up to 80 carbon atoms, preferably up to 50, or 32, or 30, or 28, or 26, or 24 carbon atoms.

In some preferred embodiments, R ^{1 is} preferably a C ₅ -C ₂₀ alkyl group, preferably a C ₅ -C ₁₅ alkyl group, preferably a C ₆ -C ₁₂ alkyl group, preferably C ₇ - C ₁₁ alkyl, preferably C ₈ - C ₁₀ alkyl, more preferably C ₉ alkyl.

In certain preferred embodiments, R ^{1 is} preferably C ₁₂ -C ₃₂ alkyl, preferably C ₁₆ -C ₂₈ alkyl, preferably C ₂₀ -C ₂₄ alkyl.

In one aspect, R ¹ is a branched alkyl group, preferably a C _3-6 branched alkyl group, for example t-butyl.

In one aspect, R ¹ is a linear alkyl group.

In a preferred aspect, R ¹ is para-substituted with respect to the OH group.

In a preferred aspect of, C _n H _2n group substituted with an OH group with respect to overall.

Preferably, R ¹ is para-substituted with respect to the OH group and the C _n H _2n group(s) are substituted in the order of the OH group.

Preferably, R ² is hydrogen. Preferably, R ³ is hydrogen. Preferably, both R ² and R ³ are hydrogen. In a specific example where R ^{2 is} not hydrogen, R ^{2 is} preferably a linear or branched alkyl group which is optionally substituted. In a specific example where R ^{3 is} not hydrogen, R ^{3 is} preferably a linear or branched alkyl group which is optionally substituted.

The term "hydrocarbyl" as used in this context means any of an alkyl group, an alkenyl group, an alkenyl group, or a fluorenyl group, and the group may be a straight chain, a branched chain or a cyclic group, or an aryl group. The term hydrocarbyl also includes such groups, but wherein they have been selectively substituted. If the hydrocarbyl group is a branched structure having a substituent(s) thereon, the substitution may be on the hydrocarbon backbone or on the branch; or the substitution may be on the hydrocarbon backbone and on the branch.

In this particular embodiment, it is preferred that R ² and/or R ³ are alkyl groups independently selected from the group consisting of C ₁ -C ₅₀ groups, preferably C ₁ -C ₄₀ groups, preferably C ₁ - A C ₃₀ group, preferably a C ₁ -C ₂₅ group, preferably a C ₁ -C ₁₅ group.

A typical example of R ² or R ³ is a tertiary alkyl group such as a tertiary butyl group.

In a preferred embodiment, R ² and R ³ are substituents (rather than hydrogen) such that ring A is completely substituted.

In a preferred embodiment, the phenolic resin is a substituted phenolic resin. More preferably, the phenolic resin is the reaction product of a substituted phenol and an aldehyde.

More preferably, the phenolic resin is the reaction product of a substituted phenol and an aldehyde having 1 to 22, preferably 1 to 7 carbon atoms, for example, formaldehyde.

In a preferred embodiment, the phenolic resin is a C ₉ -C ₂₄ phenolic resin.

More preferably, the phenol resin is a reaction product of C ₉ -C ₂₄ phenol and formaldehyde, or tertiary butyrol and an aldehyde having 1 to 22, preferably 1 to 7, carbon atoms, for example, formaldehyde.

Alkoxylated phenolic resins (ethoxylated and/or propoxylated) can be obtained. The use of these is not excluded, but is not preferred because excellent results have been obtained using non-alkoxylated phenolic resins.

Fuel antioxidant as stabilizer (iii)

Fuel instability can be fueled by oxidation of fuel, or components within the fuel. This is a major issue in biofuels.

Compounds suitable for use as stabilizer (iii) in this case include antioxidants for use in fuel environments.

Antioxidants suitable as stabilizers of the present invention include phenolic antioxidants, sulfurized phenolic antioxidants, and aromatic amine antioxidants.

Preferred phenolic antioxidants are hydrocarbon-soluble phenolic antioxidants and especially those in which at least one of the phenols is blocked. Suitable antioxidants include those of the following formula:

Wherein R ¹ , R ² , and R ³ are the same or different and each is alkyl, aryl, alkylaryl, arylalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkylaryl, hydroxyaryl Alkyl, or heteroalkyl, aryl, alkylaryl, arylalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkylaryl, hydroxyarylalkyl containing nitrogen, sulfur, or oxygen and wherein At least one of R ¹ and R ² provides a steric obstacle. R ¹ and/or R ^{2 are} preferably isobutyl or tert-butyl. The barrier phenol is preferably 2,6-di-tertiary-butyl-4-methylphenol or 6-tertiary-butyl-2,4-xylenol. Further preferred examples include 2-trisylbutanol, 2-ethyl-6-cresol, 2,6-di-tertiary-butanol, 2,6-di-tris-butyl-4- Cresol, 2,2'-methylene-bis-4,6-di-tertiary butyl phenol, 4,4'-methylene-bis(2,6-bis-tertiary butyl phenol) and 2, 2'-propylene-bis(6-tris-butyl-4-cresol). Mixtures of such antioxidants can also be used.

Also useful as stabilizers are sulfides of the formula R ⁴ -S--R ⁵ and phosphine compounds of the formula PR ⁶ R ⁷ R ⁸ wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ is the same or different and each is alkyl, aryl, alkylaryl, arylalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkylaryl, hydroxyarylalkyl, or heteroalkyl, Aryl, alkylaryl, arylalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkylaryl, hydroxyarylalkyl containing nitrogen, sulfur, or oxygen.

In addition, the compounds mentioned below as biofuel instability inhibitors can also be used as fuel antioxidants.

Low temperature flow improver as stabilizer (iii)

Compounds suitable for use as stabilizer (iii) in this case include low temperature flow improvers.

The low temperature flow improver can act on the fuel, especially a fuel that solidifies under ambient conditions (for example, diesel) to maintain a flow condition under conditions that would cause solidification to occur and the fuel to become unstable.

Low temperature flow improvers useful as stabilizers in the present invention include copolymers of an alkene and an unsaturated ester, an alkyl methacrylate polymer, a polyalkoxy group Esters, ethers, esters/ethers, and mixtures thereof.

Examples of the copolymer of an alkene and an unsaturated ester include an ethylene-unsaturated ester copolymer. It is preferred that these have - in addition to units derived from ethylene - the following formula - CR ¹ R ² -CHR ³ -

Wherein R ¹ represents hydrogen or methyl; R ² represents COOR ⁴ , wherein R ⁴ represents a straight chain having 1 to 9 carbon atoms, or a branched alkyl group having 3 or more carbon atoms, or R ² represents OOCR ⁵ , wherein R ⁵ represents R ⁴ or H; and R ³ represents H or COOR ⁴ . These may comprise copolymers of ethylene and ethylenically unsaturated esters, or derivatives thereof. An example is a copolymer of ethylene and an ester of a saturated alcohol and an unsaturated carboxylic acid, but preferably, the ester is an ester of an unsaturated alcohol and a saturated acid. Ethylene-vinyl ester copolymers are advantageous; ethylene-ethylene acetate, ethylene-ethylene propionate, ethylene-ethylene hexanoate, or ethylene-ethylene octanoate copolymer are preferred. Preferably, the copolymer contains 5 to 40% by weight of vinyl ester, more preferably 10 to 35% by weight of vinyl ester. Mixtures of two or more such copolymers may be used, for example as described in U.S. Patent No. 3,961,91 . The number average molecular weight of the copolymer - measured by vapor phase osmometry - is advantageously from 1,000 to 10,000, preferably from 1,000 to 5,000. If desired, the copolymer may contain units derived from other comonomers, such as trimers, tetramers or higher polymers, for example, other comonomers are isobutylene or isobutylene. The copolymer can be prepared by direct polymerization of a comonomer, or by transesterification of an ethylenically unsaturated ester copolymer, or by hydrolysis and reesterification to form a different ethylenically unsaturated ester copolymer. For example, ethylene-ethylene hexanoate and ethylene-ethylene octanoate copolymers can be prepared in this manner, for example, from ethylene-ethylene acetate copolymers.

Examples of alkyl (meth) acrylate polymers useful as low temperature flow improvers include from 10 to 95 mol% of one or more alkyl acrylates or alkyl methacrylates (with C ₁ - to C ₂₆ - an alkyl chain) and from 5 to 90 mol% of a copolymer of one or more ethylenically unsaturated dicarboxylic acids or anhydrides thereof, which have been thoroughly reacted with one or more primary or secondary amines to form two Monodecylamine or guanamine/ammonium salt of a carboxylic acid. The copolymer preferably contains 10 to 95, preferably 40 to 95, and most preferably 60 to 90, mol% of one or more alkyl (meth) acrylates and 5 to 90, preferably 5 to 60, and Most preferably from 10 to 40, mol% of one or more ethylenically unsaturated dicarboxylic acids or anhydrides. The alkyl group of the alkyl (meth) acrylate has, for example, 1 to 26, preferably 4 to 22, and most preferably 8 to 18 carbon atoms. The alkyl group is preferably straight chain and unbranched. However, up to 20% w cyclic and/or branched alkyl components may be present. Examples of particularly preferred alkyl (meth) acrylates include n-octyl (meth) acrylate, n-fluorenyl (meth) acrylate, n-dodecyl (meth) acrylate, N-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof. Examples of ethylenically unsaturated dicarboxylic acids are, for example, maleic acid, tetrahydrofurfuric acid, citraconic acid and itaconic acid and anhydrides thereof, and fumaric acid. Maleic anhydride is preferred.

Examples of polyalkylene oxide esters, ethers, esters/ethers or mixtures thereof which can be used as a low-temperature flow improver include those having at least two C ₁₀ to C ₃₀ linear saturated alkyl groups and having a molecular weight of from 200 to 2,000. In the case of an alkoxyethylene glycol, the alkylene group of the polyalkylene glycol has from 1 to 4 carbon atoms.

Wax anti-settling agent as stabilizer (iii)

Compounds suitable for use as stabilizer (iii) in this case include wax anti-settling agents.

The wax anti-settling agent acts on the fuel, especially a fuel that solidifies under ambient conditions (for example, diesel) to maintain a flow state under conditions that cause solidification to occur and the fuel to become unstable.

The wax anti-settling agent used as a stabilizer in the present invention includes certain polyamidiene and maleic anhydride olefin copolymers.

Suitable maleic anhydride olefin copolymer additives can be prepared by the reaction of maleic anhydride and alpha-olefin. Typically such copolymer additives preferably comprise maleic anhydride and alpha-olefin in substantially equal molar numbers. The starting alpha-olefin being operated is a mixture of individual alpha-olefins having a range of carbon numbers. Α- olefin starting composition for the preparation of maleic anhydride-olefin copolymer additive of the present invention have a carbon number of about C ₂₀ to about C ₄₀ α- olefin of at least a minimum weight concentration. The additive typically contains a blend of alpha-olefins having carbon numbers in this range. The starting alpha-olefin being manipulated may have a minor portion of the component that falls outside of the above carbon number range. The maleic anhydride alpha-olefin copolymer has a numerical average molecular weight of from about 1,000 to about 5,000 as measured by vapor pressure osmometry. Also suitable are wax anti-settling additives comprising an alkylamine, a maleimide reacted with an alpha-olefin to produce a quinone imine. Typically, the quinone imine is produced from a maleic anhydride and an alpha olefin which are substantially equal in moles. The alpha olefin being manipulated is similar in composition to the above description of the maleic anhydride olefin copolymer additive. A particularly advantageous property is obtained when the alkylamine is tallow amine. The quinone imine preferably has a numerical average molecular weight of from about 1,000 to about 8,000 as measured by vapor pressure osmometry.

Suitable stabilizers include the following additives:

Wherein R has at least 60% by weight of a hydrocarbon substituent of from about 20 to about 40 carbons, and n is from about 2 to about 8. Preferably, R has at least 70% by weight of a hydrocarbon substituent of from about 20 to about 40 carbons, and most preferably, R has at least 80% by weight of a hydrocarbon substituent of from about 20 to about 40 carbons. In a preferred embodiment, R has at least 60% by weight of a hydrocarbon substituent having a carbon number of from 22 to 38 carbons, more preferably at least 70% by weight, and most preferably at least 80% by weight. The resulting maleic anhydride alpha-olefin copolymer has a numerical average molecular weight of from about 1,000 to about 5,000 as measured by vapor pressure osmometry.

The following stabilizers can also be used:

Wherein R has at least 60% by weight of a hydrocarbon substituent of from about 20 to about 40 carbons, and R' has at least 80% by weight of a hydrocarbon substituent of from 16 to 18 carbons, and n is from about 1 to about 8. Preferably, R has at least 70% by weight of a hydrocarbon substituent of from about 20 to about 40 carbons, and most preferably R has at least 80% by weight of a hydrocarbon substituent of from about 20 to about 40 carbons. In a preferred embodiment, R has at least 60% by weight of a hydrocarbon substituent carbon having a carbon number of from 22 to 38 carbons, more preferably at least 70% by weight and most preferably at least 80% by weight. Typically, R' has at least 90% by weight of 16 to 18 carbon hydrocarbons Substituent. The additive described above as a quinone imine has a numerical average molecular weight of from about 1,000 to about 8,000 as measured by a vapor pressure osmosis method.

Further compounds which are claimed to be useful as wax anti-settling agents and/or low temperature flow inhibitors are described in EP-A- 743 972 and EP-A- 743 974, the contents of each of which are incorporated herein by reference.

Biofuel instability inhibitor as stabilizer (iii)

Compounds suitable for use as stabilizer (iii) in this case include biofuel instability inhibitors. These utilities are polymers or high molecular weight compounds that are primarily dispersed in biofuels and are by-products of oxidation or thermal cracking. A list of unrestricted chemicals that can be used to perform this function includes the following polymers: ethylene and unsaturated esters; vinyl alcohol, vinyl ether and esters thereof with organic acids; propylene, ethylene, isobutylene adducts and unsaturated carboxylic acids Acids (such as maleic acid and fumaric acid) and their guanamine or quinone derivatives; acrylic acid and its guanamine or ester derivatives; polystyrene; and polymers made from such monomer combinations. In addition, the compounds mentioned above as fuel antioxidants can also be used as biofuel instability inhibitors.

Blending fuel or separation inhibitor as stabilizer (iii)

Compounds suitable for use as stabilizer (iii) in this case include blended fuel separation inhibitors.

The fuel blending separation inhibitor in this case acts to maintain two or more fuels in a dispersed or blended form. Loss of fuel uniformity and fluidity may also occur when there is phase separation within such fuels. When the ship is docked and purchases any fuel available in the area at the desired price, the fuel blend is typically produced in the sump. When mixing two or more different distillation fuels, or when When biofuels and distillate fuels are blended, for example, stability may be lost.

Many of the compounds which are inhibitors of the fuel blend separation include the above-mentioned compounds as stabilizers of other types, and need not be repeated here.

Another possible type of useful compound that achieves the benefits of the present invention is a fuel cleaner, which is well known to those skilled in the art. The detergent may be used as component (iii) by itself or may be used outside of another stabilizer.

Additive composition

In a preferred embodiment, in the additive composition, the metal compound (i) is biscyclopentadienyl iron, the organic compound (ii) is camphor and the stabilizer (iii) is a C _8-24 alkyl substituted phenol and The reaction product of an aldehyde is preferably a reaction product of a C _9-20 alkyl-substituted phenol and formaldehyde.

Preferably, the additive composition is a liquid. The additive composition may in turn comprise a diluent.

It is expedient if the additive composition is added as a solution of the active ingredient placed in the diluent. Preferably, such solutions exhibit a high concentration of active ingredient in the diluent. The diluent used should be readily soluble in the fuel and compatible with the fuel, including the boiling point range, preferably having a flash point in excess of 62 ° C for storage. Desirable diluents are those which dissolve all active ingredients as well and form a solution which undergoes a long shelf life and is stable under ice cold conditions.

However, the present invention does not exclude additive compositions in solid form (or ingredients thereof, if provided separately).

Preferred additive compositions comprising the three components (i), (ii) and (iii) comprise: 3-1000 parts (i), preferably 10 to 500 parts (i), preferably 50 to 200 parts (i), Preferably, 100 parts (i) are 3 to 600 parts (ii), preferably 10 to 200 parts (ii), preferably 20 to 100 parts (ii), preferably 35 to 70 parts (ii) and 1 on top. To 10,000 parts (iii), preferably 15 to 300 parts (iii), preferably 30 to 150 parts (iii); preferably 50 to 120 parts (iii).

When the additive combination is intended to be added as an "aftermarket" treatment, the volume of diluent used will be convenient for providing a non-sticky liquid suitable for dispensing or injecting packaging.

Preferably, the diluent is selected from the group consisting of aromatic compounds, hydrocarbon compounds, and mixtures thereof. In general, the diluent may be a crude oil distillation product selected from the group consisting of kerosene, cracked gas oil, vacuum gas oil, long residue, short residue, heavy petroleum brain, light weight Gas oil, medium gas oil, heavy gas oil, recovered oil, gasoline, oil, and mixtures thereof.

The diluent can be a "paraffin compound" which can include both linear and branched compounds. Branched compounds are also known as isoparaffins.

Preferably, the diluent is a vacuum gas oil. In a preferred aspect, the diluent is a light vacuum gas oil. The term "light vacuum gas oil" generally means a gas oil fraction obtained from a vacuum distillation column which typically has a boiling point of from 350 to 630 °C.

Although it is not excluded to separately add ingredients (ie, (i) + (ii) + (iii); or (i) / (ii) + (iii); or (i) / (iii) + (ii); or (ii ) / (iii) + (i)) and in some cases is convenient, but it is envisaged that components (i), (ii) and (iii) will be either additive compositions or contain individual components - ie (i) /(ii)/(iii)- The set is added.

The advantages of the additive composition are quite obvious. The fuel without added additive can be modified into a fuel composition according to the present invention by homogenizing it by adding a corresponding amount of the additive composition to the hydrocarbon mixture and preferably mixing. It is also possible to add the corresponding amounts of ingredients (i), (ii) and (iii) to the mixture, respectively. However, it is necessary not only to ensure the concentration of each individual in the fuel, but also to ensure the correct relationship between the individual components. It is therefore relatively simple and more customer-friendly to provide an additive composition that already contains components that are in a proper relationship with each other.

fuel

In one aspect of the invention, the fuel system is preferably selected from the group consisting of biofuels, diesel, gasoline, marine fuel, bottom fuel, residual fuel, heating oil, medium distillate oil and heavy fuel oil; and includes GTL (liquefied gas) ), CTL (liquefied coal), BTL (liquefied biomass), and OTL (liquefied oil sand). The fuel may be a blended fuel, such as a blend of petroleum fuel and biofuel (for example, conventional diesel and biodiesel); or a blend of distilled fuel and different distillation fuels. However, this fuel list is considered to be unlimited.

In still another aspect, the fuel is a medium distilled oil or a heavy fuel, which is a marine fuel, a bottom fuel, or a heating oil.

The fuel can be a gas oil or a heating oil, including recycled light heating oil.

The marine fuel can be marine diesel fuel, marine distilled fuel or marine gas oil.

Preferably, the fuel is a liquid having a viscosity of at least 1 cSt, preferably at least 10 cSt, preferably at least 80 cSt, preferably at least 100 cSt, preferably at least 120 cSt. In some specific examples of the use of marine fuel, the viscosity at 40 ° C can be at least 360 cSt, preferably 450 cSt.

Preferably, the fuel is a liquid having a viscosity of at most 1000 cSt, at most 800 cSt, preferably at most 700 cSt, preferably at most 600 cSt, preferably at most 560 cSt, preferably at most 520 cSt at 40 °C.

For this viscosity definition in this specification, the reference temperature is 40 ° C and the viscosity is measured by the ISO 3104:1994 procedure.

Fuel composition

Preferably, the fuel composition comprises at least 3 ppm of metal compound (i), preferably at least 5 ppm, preferably at least 10 ppm, preferably at least 15 ppm, preferably at least 20 ppm.

Preferably, the fuel composition contains 1000 ppm or less of the metal compound (i), preferably 400 ppm or less, preferably 200 ppm or less, preferably 100 ppm or less, preferably 50 ppm or less.

Preferably, the fuel composition comprises a metal compound (i) in an amount sufficient to provide at least 0.1 ppm of metal, preferably at least 2 ppm, preferably at least 3 ppm, preferably at least 6 ppm.

Preferably, the fuel composition comprises a metal compound (i.e., which provides 350 ppm or less of metal, preferably 140 ppm or less, preferably 60 ppm or less, preferably 30 ppm or less, preferably 15 ppm or less. ).

In case, for example, the metal compound (i) is ferrocene, 30 ppm of ferrocene is a portion sufficient to provide about 10 ppm of metal (iron). Thus, if the fuel composition contains a metal compound (i) in an amount sufficient to provide 10 ppm of metal, it is present in an equivalent amount of 30 ppm ferrocene.

Preferably, the fuel composition comprises at least 1 ppm of organic compound (ii), preferably at least 3 ppm; preferably at least 5 ppm, preferably at least 8 ppm, It is preferably at least 12 ppm.

Preferably, the fuel composition contains 600 ppm or less of the organic compound (ii); preferably 200 ppm or less, preferably 100 ppm or less; preferably 50 ppm or less, preferably 25 ppm or less.

Preferably, the fuel composition contains at least 0.1 ppm of stabilizer (iii), preferably at least 1 ppm, preferably at least 5 ppm, preferably at least 10 ppm, preferably at least 15 ppm, preferably at least 18 ppm, and preferably at least 20 ppm.

Preferably, the fuel composition contains 1000 ppm or less of stabilizer (iii), preferably 320 ppm or less, preferably 160 ppm or less, preferably 80 ppm or less, preferably 40 ppm or less.

According to the present invention, there is provided a fuel composition comprising a fuel comprising:

(i) a metal compound of from 3 to 1000 ppm (preferably from 5 to 400, preferably from 10 to 200 ppm, preferably from 15 to 100 ppm, preferably from 20 to 50 ppm) selected from the group consisting of iron compounds, manganese compounds, calcium compounds, antimony compounds, And mixtures thereof; (ii) from 1 to 600 ppm (preferably from 3 to 200 ppm, preferably from 5 to 100 ppm; preferably from 8 to 50 ppm, preferably from 12 to 25 ppm) of an organic compound selected from the group consisting of bicyclic monoterpenes, substituted bicyclic rings Monoterpene, adamantane, propylene carbonate, and mixtures thereof; and (iii) 0.1 to 1000 ppm (preferably 1 (or 5, or 10) to 320 ppm, preferably 15 to 160 ppm, preferably 18 to 80 ppm, preferably 20 Stabilizer up to 40 ppm).

The concentration of components (i), (ii) and (iii) in the fuel composition is in principle the amount of individual component (i), (ii) or (iii) added (referred to as the treat rate). And the sum of any parts of the corresponding ingredients that are already present in the fuel, whether natural or separately. Separate additions can be used as part of an additive kit for different purposes, for example.

In most practical situations, however, the concentration of the components present is substantially equal to the treatment ratio and the above definitions of the concentrations of components (i), (ii) and (iii) within the fuel composition can be considered as added to The amount of fuel; that is, the treatment ratio.

In the present specification, the amount used in describing the ingredients is always by weight.

According to the invention, the components - preferably the additive composition - can be added to the fuel before or during combustion. This addition may be made at any stage of the fuel supply chain (for example, refining or dispensing end) or may be via a feeding device connected to, for example, a combustion system on board. If a charging device is used, it may be added to the fuel or may even be added directly to the combustion chamber or inlet system, respectively. The user can add fuel to the fuel tank of the combustion system; the so-called "after-sales maintenance" treatment.

Preferably, most of the hydrocarbons contained in the hydrocarbon mixture are petroleum derived. However, the hydrocarbon mixture may also contain other natural or recycled materials such as, for example, rapeseed oil methyl ester. Biofuels can be used.

Additional additive

The additive concentrate and/or fuel may in turn comprise additional additives, such as performance enhancing additives. A non-limiting list of such additional additives includes corrosion inhibitors, rust inhibitors, gel inhibitors, mineral spirits, antistatic agents, dyes, anti-caries agents and detergents.

Combustion System

Preferably, the combustion system is selected from the group consisting of a burner, an engine, and a furnace.

Preferably, the combustion system is selected from the group consisting of a burner and a furnace.

Preferably, the combustion system is an engine, preferably a ship's engine. Preferably, the engine is a compression ignition engine (diesel engine).

Advantage

The additive composition allows for the successful use of fuels that have a relatively high viscosity and that previously tend to separate and burn "dirty" during transport or storage (resulting in coke and aerosol-like exhaust gases from the engine section and the exhaust equipment).

Specific benefits include: Stabilizing fuel (even if it is blended), including maintaining for efficient delivery and Appropriate characteristics of combustion; reduce soot content and ash content of combustion system discharge; reduce maintenance downtime, long operating period between downtimes; improve combustion efficiency of combustion system; improve fuel economy of combustion system; A fuel that was previously considered unsuitable, or previously considered unsuitable for blending with fuel already present in the fuel tank; capable of using any fuel available on the market at a given time.

In this specification, the preferred features of any aspect are preferred features of all other aspects, unless a particular condition or background renders it unfeasible.

An illustration of the invention

The invention will now be further illustrated by reference to the following specific examples.

The following compositions are used as additives to fuels under confidential conditions To the ship, for six months. The fuel is a blended marine fuel having a viscosity of 140 cSt (measured at 40 ° C in accordance with the ISO 3104:1994 procedure). Previously the ship was operated with marine fuel at 60 cSt (measured at 40 ° C in ISO 3104:1994 procedure). 140 cSt fuel - more viscous than 60 cSt - contains more impurities and tends to separate or settle during storage and forms soot combustion, which may leave residual coal char deposits in the engine and downstream, especially in heat recovery equipment, causing it Serious efficiency loss or failure; and it may also appear as a smoke effluent.

Ferrocene - added to marine fuel at a concentration of 30ppm ferrocene

Camphor - add marine fuel at a concentration of 15ppm camphor

(provided in a solvent soluble in hydrocarbon)

Stabilizers, i.e. C ₂₀ - ₂₄ alkyl phenol and formaldehyde, the ester reaction product - ester at a concentration of 25ppm ocean added fuel (to provide soluble in hydrocarbon solvents).

The ship is a mixed passenger/cargo ship with a total tonnage of 6,090 tons. The ship has two Mitsubishi Mon 18V 40/54 main engines, each for more than 30 years and tends to smoke. The rated speed is 20,000 Ps / 430 rpm. The average fuel consumption is about 825 liters per vehicle 380 cSt marine fuel per hour. The ship has three Daihatsu 6PSHTc-26D auxiliary engines. The rated speed is 765 Ps/720 rpm. The average fuel consumption is 100 liters per hour per auxiliary engine.

The ship was chosen because after the test was over, the ship was scheduled to tip over into the dry dock.

The composition is added to the fuel tank in a calculated amount each time the vessel adds another 140 cSt of fuel.

The nature of the test - real life sea trials rather than laboratory tests - means "scientific" information that does not have soot content, ash content, etc. another On the other hand, the empirical observation of the test results at sea for six months has a "real life" value.

140 cSt fuel that is not assigned to perform tasks is less expensive than 60 cSt fuel.

It was observed that the additive allowed 140 cSt of fuel to be used without replacing the 60 cSt fuel. The additive appears to render the fuel in a suitable fluid without sedimentation or separation and to prevent/inhibit the formation of unwanted soot and ash.

No adverse effects were noticed on any of the engine sections, fuel injection pumps, superchargers or heat recovery equipment during the test.

And the vent gas system is relatively clean. In fact, the old engine on board the ship used for this test, without marine fuel, produced completely clean emissions. Even 60 cSt fuel will generate some smoke. It was observed that the additive-free 140 cSt fuel produced a smoke-like effluent, but the 140 cSt fuel with the additive produced less smoke-like effluent than the 60 cSt fuel - a very impressive result. I believe that a modern engine can be used to obtain clean emissions.

Moreover, the 140 cSt fuel has a higher energy rating than the 60 cSt fuel, so the average fuel consumption is reduced by 10% from 825 per hour per hour to 750 liters per main engine. This represents a significant cost savings in addition to the cost per ton of fuel purchased.

I think these results are amazing. It was originally expected to have some negative effects to balance the positive economic benefits of using this cheaper, heavier fuel.

Second example of the invention - heating fuel test

Test Equipment

Steel heating boiler: Ruhr Brenner, model B 4T/14021kW, year of manufacture 1996

Heat output: set to 20kW

Oil burner: Ruhr Brenner, model RH-4, 12-45 kW, year of manufacture 1996

Injector (nozzle): Danfoss Typ H, 0.50 US gallons per hour (1.87 kg/h), 6O ⁰ H

⁰ H is the indexing angle / spray index, hollow cone

Smoke tester Brigon smoke tester.

In the test, the burner pump was set to a single line mode, which prevented the oil from flowing back to the vessel and was thus heated by the burner pump.

The change from one test fuel to another test fuel system was achieved by switching the three-way valve directly in front of the burner. Thanks to the three-way valve and single-wire circuit, it is ensured that incorrect measurements due to additive residues in the line do not occur. Individual soot measurement systems were introduced using Bacharach soot pumps and evaluated by visual observation and measurement with soot number test equipment.

Second example - specific example A

The steel hot water boiler is raised to operating temperature with a heating oil without additives and without any biofuel. The number of smoke spots is set to about 3 by controlling the air entering the burner.

The test lasted for approximately 0.75 hours and then the number of smoke spots was measured.

Then, this burner was used to test the heating oil containing biofuel and rapeseed oil to measure the influence of the biofuel component.

The number of soot is measured by evacuation (pushing through the filter mat with a manual smoke tester with a specific portion of the gas volume). The filter mat was visually judged (by comparison) after measurement. The average number of soots is the result of 10 individual measurements.

Second example - specific example B

In this specific example, the effect of the additive on the fuel containing the biofuel component is measured. Using the same equipment and operating procedure as "Second Example, Specific Example B", the initial number of spots of the heating oil without additives but containing 5% biofuel (net oil methyl ester) is adjusted by the burner Just set a measurable smoke point and set it to about 3.

The same fuel containing the additives A and B (addition ratio of 1 liter of additive to 2000 liters of fuel) as defined below was then tested.

Additive A

When added at the above addition ratio, the additive added to the hydrocarbon solvent is administered in combination with the following active ingredients:

Ferrocene: 0.5ppmw/w

Camphor: 40ppmw/w

Stabilizer 1: 20ppmw/w-copolymer of lauryl methacrylate and dimethylaminoethyl methacrylate

Stabilizer 2: 37ppmw/w - a mixture of mono-, di- and para-tertiary butanol

Stabilizer 3: 17ppmw/w-2,6-di-tertiary butyl-4-cresol

Additive B

When added at the above addition ratio, the additive added to the hydrocarbon solvent is administered in combination with the following active ingredients:

Ferrocene: 0.5ppmw/w

Camphor: 40ppmw/w

Stabilizer 1: 20ppmw/w-copolymer of lauryl methacrylate and dimethylaminoethyl methacrylate

Stabilizer 2: 37ppmw/w-mixture of mono-, di- and gin-tertiary butyl phenol

Stabilizer 3: 17ppmw/w-2,6-bis-tertiary-butyl-4-cresol

Stabilizer 4: 118ppmw/w - low temperature flow improver ethylene vinyl acetate copolymer

Stabilizer 5: 22.5 ppmw/w-treated olefin maleic anhydride copolymer (wax anti-settling agent)

A third example of the invention - marine fuel testing

Test Equipment

Engine type: Caterpillar 6 M20 (formerly MAK)

Technical Information

Test Conditions

In these tests, the engine was operated at a constant speed of 1000 rpm under various load conditions between 0 kW and 850 kW.

fuel

Fuel analysis

. Fuel 1 "clean" test fuel blend prepared by diluting 580 cSt blended stock oil with marine diesel fuel to give fuel with a CCAI of 821 and a viscosity of approximately 85 cSt at 40 °C

. Fuel 2 "dirty" test fuel blend prepared by diluting the same 580 cSt blended stock oil with light recovery oil to give a fuel with a CCAI of 856 and a viscosity of approximately 275 cSt at 40 °C

. Fuel 3 is the same fuel blend as Fuel 2, but contains the following additive kits.

Additive composition

Ferrocene - added to fuel 3 at a concentration of 33 ppm ferrocene

Camphor - added to fuel 3 at a concentration of 13ppm camphor

(provided in a solvent soluble in hydrocarbon)

The dispersant, that is, the ester reaction product of C20-24 alkylphenol and formaldehyde, was added to Fuel 3 (provided in a hydrocarbon solvent) at a concentration of 25 ppm ester.

measuring

The following measurements were taken:

Emissions

Microparticles (mg microparticles per kg of effluent)

Total hydrocarbons (ppm, FID)

Oxygen (% by volume in the effluent, paramagnetic resonance analysis)

Carbon monoxide (ppm by volume in the effluent, IR absorption)

Heat release (J/∘) vs crank angle (∘)

Emissions

These results indicate that fuel 3 produces a lower particulate level than fuel 2 when the engine is idle at high power and especially at zero load conditions. Furthermore, fuel 3 burns more completely than fuel 2, especially at low loads.

Heat release (J/∘) vs crank angle (∘)

The fuel was injected at 14.5 inches before the top dead center of the wheel. The heat release plots the crank angle and then gives a measure of the ignition delay.

The heat release curve shows that under these load conditions, the "dirty" fuel 2 has a significantly longer and undesired ignition delay than the "clean" fuel 1.

The added fuel 3 has an improved ignition delay compared to the fuel 2.

This effect is expected to be most pronounced during start-up, warm-up, and low load or idle conditions.

Figure 1 shows this plot of three fuels under low load conditions (0 kW).

Claims (37)

An additive composition for a hydrocarbon fuel, comprising: (i) a metal compound selected from the group consisting of an iron compound, a manganese compound, a calcium compound, a cerium compound, and a mixture thereof; and (ii) an organic compound selected from the group consisting of bicyclic monoterpenes a substituted bicyclic monoterpene, adamantane, propylene carbonate, and mixtures thereof; and (iii) a stabilizer; wherein the (iii) stabilizer comprises a bituminous dispersant, a low temperature flow improver, a wax a mixture of settlers or the like. An additive composition for a hydrocarbon fuel, comprising: (i) a metal compound selected from the group consisting of an iron compound, a manganese compound, a calcium compound, a cerium compound, and a mixture thereof; and (ii) an organic compound selected from the group consisting of bicyclic monoterpenes a substituted bicyclic monoterpene, adamantane, propylene carbonate, and mixtures thereof; and (iii) a stabilizer; wherein the (iii) stabilizer is selected from the group consisting of phenolic resins, including di-(C1- a copolymer of a C4 alkyl)amino (C1-C4 alkyl) acrylate or methacrylate unit, a copolymer of an alkene and an unsaturated ester, an alkyl methacrylate polymer, a polyalkylene oxide ester , an ether or ester/ether, a maleic anhydride olefin copolymer additive prepared by the reaction of maleic anhydride and an α-olefin, The quinone imine produced by the reaction of an alkylamine, maleic anhydride and an α-olefin. An additive composition according to claim 1 or 2, which comprises components (i), (ii) and (iii) in the following relative parts by weight: from 3 to 1000 parts (i), from 3 to 600 parts ( Ii), and 1 to 10,000 parts (iii). The additive composition of claim 3, wherein the component (i) is in an amount of from 10 to 500 parts by weight. The additive composition of claim 3, wherein the component (i) is in an amount of 50 to 200 parts by weight. The additive composition of claim 3, wherein the relative weight portion of the component (i) is 100 parts. The additive composition of claim 3, wherein the component (ii) is in an amount of from 10 to 200 parts by weight. The additive composition of claim 3, wherein the component (ii) is in an amount of from 20 to 100 parts by weight. The additive composition of claim 3, wherein the relative weight portion of the component (ii) is 35 to 70 parts. The additive composition of claim 3, wherein the relative weight portion of the component (iii) is from 15 to 300 parts. The additive composition of claim 3, wherein the relative weight portion of the component (iii) is from 30 to 150 parts. The additive composition of claim 3, wherein the relative weight portion of the component (iii) is 50 to 120 parts. Such as the additive composition of claim 1 or 2, which is provided with Iron complex as component (i), the iron complex is selected from the group consisting of bis-cyclopentadienyl iron; substituted bis-cyclopentadienyl iron; per-alkali iron soap; and mixtures thereof. An additive composition as claimed in claim 13 wherein ferrocene is provided as component (i). An additive composition according to claim 1 or 2, wherein the following is provided as component (ii): a bicyclic monoterpene or a substituted bicyclic monoterpene selected from the group consisting of camphor, camphene, isodecyl acetic acid Esters, dipropylene glycol-isodecyl ether, adamantane, propylene carbonate; and mixtures thereof. An additive composition as claimed in claim 15 which provides camphor as component (ii). The additive composition of claim 1 or 2, wherein the stabilizer (iii) is a low temperature flow improver. The additive composition of claim 1 or 2, wherein the stabilizer (iii) is a wax anti-settling agent. The additive composition of claim 1 or 2, wherein the stabilizer (iii) is a fuel antioxidant. An additive composition according to claim 1 or 2, wherein the stabilizer (iii) is a blended fuel separation inhibitor. An additive composition according to claim 1 or 2, wherein the stabilizer (iii) is a biofuel instability inhibitor. The additive composition of claim 1 or 2, wherein the stabilizer (iii) is an asphalt fine dispersant. The additive composition of claim 22, wherein the stabilizer (iii) is a phenolic resin of the formula (xi): Wherein m is at least 1; wherein n is at least 1; wherein the or each of R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl, aromatic and heterocyclic, or may be OH, hydrocarbyl, oxygen Base hydrocarbon group, -CN, -NO ₂ , -SO ₃ H, -SO ₂ H, -COOH, -COOR ⁴ , -NH ₂ , -NHR ⁵ , -SO ₂ NH ₂ , -SO ₂ , -NHR ⁶ , CONH ₂ , CONHR ⁷ , SH and halogen; wherein each of R ⁴ , R ⁵ , R ⁶ and R ⁷ is independently selected from a hydrocarbon group. A fuel composition comprising an additive composition as disclosed in claims 1 to 23, and a hydrocarbon fuel. The fuel composition of claim 24, wherein the fuel is selected from the group consisting of biofuels, diesel, gasoline, marine fuel, bottom fuel, heating oil, medium distilled oil and heavy fuel oil; and includes GTL (liquefaction) Gas), CTL (liquefied coal), BTL (liquefied biomass), and OTL (liquefied oil sands); and include blends containing one or more of such fuels. A fuel composition according to claim 23 or 24, which comprises at least 3 ppm to 1000 ppm of the metal compound (i). For example, the fuel composition of claim 23 or 24 includes 1 Phen to 600 ppm of organic compound (ii). A fuel composition according to claim 23 or 24, which comprises from 0.1 ppm to 1000 ppm of a stabilizer (iii). A fuel composition according to claim 23 or 24, which comprises a hydrocarbon fuel, and: (i) 3 to 1000 ppm of a metal compound selected from the group consisting of an iron compound, a manganese compound, a calcium compound, a cerium compound, and a mixture thereof; (ii) 1 to 600 ppm of an organic compound selected from the group consisting of bicyclomonofluorene, substituted bicyclomonofluorene, adamantane, propylene carbonate, and mixtures thereof; and (iii) 0.1 to 1000 ppm of a stabilizer. A fuel composition according to claim 23 or 24, which is a liquid having a viscosity of at least 1 cSt at 40 °C. A fuel composition according to claim 30, which is a liquid having a viscosity of at least 80 cSt at 40 °C. A fuel composition according to claim 31, which is a liquid having a viscosity of at least 360 cSt at 40 °C. A fuel composition according to claim 32, which is a liquid having a viscosity of at most 1000 cSt at 40 °C. A method of combusting a hydrocarbon fuel composition in a combustion system with an exhaust pipe, the method comprising providing a fuel composition comprising: (i) a metal compound selected from the group consisting of an iron compound, a manganese compound, a calcium compound, and a cerium compound And mixtures thereof; (ii) an organic compound selected from the group consisting of bicyclic monoterpenes, substituted bicyclic rings Monoterpene, adamantane, propylene carbonate, and mixtures thereof; (iii) stabilizer; comprising a bituminous dispersant, a low temperature flow improver, a wax anti-settling agent or mixtures thereof, and (iv) a hydrocarbon fuel And burning the fuel composition. A method of combusting a hydrocarbon fuel composition in a combustion system with an exhaust pipe, the method comprising providing a fuel composition comprising: (i) a metal compound selected from the group consisting of an iron compound, a manganese compound, a calcium compound, and a cerium compound And mixtures thereof; (ii) an organic compound selected from the group consisting of bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate, and mixtures thereof; (iii) stabilizers; selected from phenolic resins a copolymer comprising a unit of an acrylate or methacrylate of a bis-(C1-C4 alkyl)amino group (C1-C4 alkyl group), a copolymer of an alkene and an unsaturated ester, an alkyl methacrylate polymer , a polyalkylene oxide ester, an ether or an ester/ether, a maleic anhydride olefin copolymer additive prepared by the reaction of maleic anhydride and an α-olefin, which is produced by reacting an alkylamine, maleic anhydride and an α-olefin An imine; and (iv) a hydrocarbon fuel; And burning the fuel composition. The method of claim 34 or 35, which is carried out with the following effects: - reducing or preventing coking on the surface of the combustion system; - reducing or preventing visible smoke of the exhaust gas; - making the fuel suitable for the combustion system (not suitable if there is no such additive); - improve the stability of the fuel during storage and / or transportation; - improve the combustion efficiency of the fuel; - improve the flow characteristics of the fuel. The method of claim 34, wherein the components (i), (ii), and (iii) are the components of the additive composition of any one of claims 1 to 22.